Plasma-Assisted Atomic Layer Epitaxy of Cubic and Hexagonal InN Films and its alloys with AlN at Low Temperatures

ABSTRACT

Described herein is a method for growing indium nitride (InN) materials by growing hexagonal and/or cubic InN using a pulsed growth method at a temperature lower than 300° C. Also described is a material comprising InN in a face-centered cubic lattice crystalline structure having an NaCl type phase.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.13/916,724 filed on Jun. 13, 2013 which in turns claims the benefit ofU.S. Provisional Application 61/661,016 filed on Jun. 18, 2012, each ofwhich is incorporated herein by reference.

BACKGROUND

Among III-nitride semiconductors, indium nitride (InN) has the smallestdirect band gap, largest electron saturation velocity and mobility, andsmallest electron effective mass. It has long been an attractivesemiconductor material for application in optical, electrical, andoptoelectronic device technologies such as solar-cells and high electronmobility and high frequency devices. The most thermodynamically stablephase of the InN is a wurtzite structure (a hexagonal phase), however,the growth of zincblende (a cubic phase) InN on InAs/GaAs has beendemonstrated at 450° C. by plasma assisted molecular beam epitaxy (MBE).Cubic InN has a smaller band gap and superior electronic properties asits lattice is isotropic and possesses lower phonon scattering.

BRIEF SUMMARY

In one embodiment, a method for growing indium nitride (InN) materials,comprises growing hexagonal and/or cubic InN using a pulsed growthmethod at a temperature lower than 300° C. The InN can consist of ahomogenous phase of either hexagonal or cubic InN.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows variation of growth rate (GR) and In/N ratio with atrimethylindium (TMI) pulse of 0.06 seconds.

FIG. 2 depicts the x-ray diffraction (XRD) peaks from three of thesamples—namely InN (60 nm) on GaN/Al₂O₃ template with T_(g)=183° C.(top) and on a-plane Al₂O₃ with T_(g)=240° C. (middle) and 183° C.(bottom)).

FIG. 3 shows a schematic of the possible structure of a face centeredcubic (fcc) InN phase and how it would align to an a-plane sapphire unitcell.

FIG. 4 depicts the variation of Al content in Al_(x)In_(1-x)N with theAlN/InN cycles ratios in the whole range of x as determined by x-rayphotoelectron spectroscopy. AlN and InN layers were grown as described.First the InN was grown on GaN and then the AlN. Number of layers of InNand AlN were varied to get required concentration of Al content;

DETAILED DESCRIPTION

Definitions

Before describing the present invention in detail, it is to beunderstood that the terminology used in the specification is for thepurpose of describing particular embodiments, and is not necessarilyintended to be limiting. Although many methods, structures and materialssimilar, modified, or equivalent to those described herein can be usedin the practice of the present invention without undue experimentation,the preferred methods, structures and materials are described herein. Indescribing and claiming the present invention, the following terminologywill be used in accordance with the definitions set out below.

As used herein, “low temperature” means temperatures lower than 300° C.,and if otherwise specified can refer to yet lower temperatures such aslower than 280° C., lower than 260° C., lower than 240° C., lower than220° C., lower than 200° C., lower than 180° C., and so on.

Indium precursors include trimethylindium (TMI) and others known in theart.

Aluminum precursor includes trimethylaluminum (TMA) and others known inthe art.

As used in this specification and the appended claims, the singularforms “a”, “an,” and “the” do not preclude plural referents, unless thecontent clearly dictates otherwise.

As used herein, the term “and/or” includes any and all combinations ofone or more of the associated listed items.

As used herein, the term “about” when used in conjunction with a statednumerical value or range denotes somewhat more or somewhat less than thestated value or range, to within a range of ±10% of that stated.

DESCRIPTION

InN layers were simultaneously grown using a Cambridge Nano Tech (CNT)Fiji 200 atomic layer deposition/epitaxy (ALE) system on a-planesapphire, semi-insulating Si(111), and GaN/sapphire templates. Sapphiresubstrates were used to ensure unambiguous characterization of theelectrical transport properties of the ALE InN layers on an insulator.Wafers were solvent cleaned and rinsed with deionized (DI) water beforeany further surface pretreatments. Si(111), GaN/sapphire, and sapphiresurfaces were pretreated with HF, HF and 15% HCl, and solvents,respectively. The growth was carried out in an ultrahigh purity (UHP)argon (Ar) ambient. After ex situ surface pretreatment, substrates weretreated with the 50 sccm N₂ plasma at 300 watts before InN growth. About150 to 1100 cycles of ALE deposition (see below) were used to synthesizeInN films on different substrates simultaneously. The values ofparameters given in this paragraph are examples, with other valuespossible.

FIG. 1 shows variation of growth rate (GR) and In/N ratio with atrimethylindium (TMI) pulse of 0.06 seconds. The GR was decreased from0.83 to 0.73 Å with increasing temperature from 160 to 183° C. Itremains constant for a small temperature window and decreases again to0.51 Å at 220° C. For T_(g) between 220-260° C., the GR remainsconstant. The temperature range between 220-260° C. is the second atomiclayer epitaxy (ALE) window. In the first low temperature ALE window theInN growth is N-rich (In/N<1) and it is In-rich (In/N>1) for the hightemperature ALE window. An In/N ratio of 2.8±0.7 has been measured onMBE grown InN (see Piper et al., J. Vac. Sci. Technol. A 23, 617(2005)). Thus, the ALE InN has better stoichiometry.

FIG. 2 depicts the XRD peaks from three of the samples—namely InN (60nm) on GaN/Al₂O₃ template with T_(g)=183° C. (top) and on a-plane Al₂O₃with T_(g)=240° C. (middle) and 183° C. (bottom)). In the bottom plot,there are a set of peaks that could be indexed to either a face centeredcubic (FCC) structure with the (200) and (400) indices, or a CsClstructure with (110) and (220) indices. Also measured were the 24 hrlong Laue diffraction (LD) patterns on this sample in transmission aswell as grazing incidence reflection mode. In both modes Laue spots wereobserved, indicating that this sample has an epitaxial nature and not apowder/polycrystalline nature. This is also confirmed with the secondorder peak in the bottom plot which has resolved in the Kα₁ and Kα₂components (inset). This peak is obtained via a 15 summation scan toenhance the signal. The FWHM values are 494 and 371 arc-secs for thefirst and second order peaks, respectively. The first order peak is aconvolution of the two Kα components. In order to confirm the structure,the third order peak was examined, which was not measurable since itoccurs at much higher angles and the sample is only 60 nm thick. Also,the d-spacings of the first two peaks do not match to any InN phases inthe ICDD database. The results suggest that the InN on a sapphire at183° C. has a highly oriented epitaxial structure. Further analysis ofthe data reveals that the d spacings (6.68 Å) of the first peak do notmatch to any of the known InN phases in the reported internationalcenter for diffraction data (ICDD) database and instead corresponds to aface centered cubic (FCC) structure which has not been reported before.The XRD data was corroborated by electron microscopy as described inCryst. Growth Des. 2013, 13, 1485-1490, incorporated herein byreference.

FIG. 3 shows a schematic of the alignment of a face centered cubic (fcc)InN phase unit cell with an a-plane sapphire substrate unit cell. Fromthe measured lattice parameter of the InN film assuming the FCCstructure, we see that it has only a 2.8% mismatch with the in-planec-direction and a 18.9% mismatch with the in-plane m-direction ofsapphire. This is further indication that this is the most likely phaseof the grown InN film on a-plane sapphire.

There has been a previous report (see ref. 21) of cubic InN growth at450° C. by plasma-assisted molecular beam epitaxy (MBE) on InAs/GaAs,but the InN is demonstrated to have a ZnS (zincblende) phase rather thana NaCl-type phase as obtained herein.

Table 1 summarizes different parameters and their values to synthesizevarious materials. Each ALE cycle consisted of first a 60 mstrimethylindium (TMI) pulse (which was empirically found as self-limitedALE growth mode, with longer pulses not providing significantly greatergrowth), which were added to a constant 30 and 100 sccm flow of UHPargon carrier gas. After each TMI pulse, the main pumping valve wasclosed for 5 sec so that the surface would saturate with In atoms. A 20second long 300 watt N₂ plasma exposure was used to provide nitrogenprecursor to the indium saturated surface. To remove unreactedprecursors, the deposition chamber was purged with UHP argon for 10 safter each pulse. The reactor chuck was heated resistively, and thetemperature was calibrated using thermocouple and by pyrometer by CNT.The values of parameters given are examples. Other values are possible.

For the ALE growth of AlInN, InN and AlN layers were grown layer bylayer in the fashion of a digital alloy. To grow Al_(0.90)In_(0.10)N,AlN and InN were grown alternatively. For an AlN for every two cycles ofInN results Al_(0.79)In_(0.21)N. For an AlN for every three cycles ofInN results Al_(0.68)In_(0.32)N. Thus by changing the combination ofnumber layers of InN and AlN, Al_(x)In_(1-x)N films can be obtained infor a wide range of x via atomic layer epitaxy. In this manner, AlInNternary alloys are realized over the entire desired stoichiometryrange—this is believed to be the first time this was accomplished. Thevalues of parameters given are examples. Other values are possible.

TABLE 1 growth parameters for ALE of InN Number of Parameters TMI PulsePurge 300 W N₂ Plasma Plasma pulse Purge cycl Studied 0.015-0.1 sec 5-15sec 50-150 sccm 10-30 sec 5-15 sec 150-1100 range Established   0.06 sec  10 sec   100 sccm   20 sec   10 sec — value

TABLE II growth parameters for ALE of AlN Parameters TMA Pulse Purge 300W N₂/H₂ Plasma Plasma pulse Purge Studied range 0.03-0.1 sec 5-40 sec N₂only-N₂:H₂ = 1:3 10-30 sec 5-40 sec Established value 0.06 sec 10 sec42/8 sccm 20 sec 10 sec

The techniques described herein are expected to provide a crystallinematerial having low oxygen impurity by ex situ and in situ surfacetreatment. Moreover, in situ surface treatment with the atomic hydrogen,nitrogen, mixture of hydrogen and nitrogen, and/or ammonia plasma ispossible. It is possible to vary purge time with the pumping speed inorder to control carbon impurities.

Concluding Remarks

All documents mentioned herein are hereby incorporated by reference forthe purpose of disclosing and describing the particular materials andmethodologies for which the document was cited.

Although the present invention has been described in connection withpreferred embodiments thereof, it will be appreciated by those skilledin the art that additions, deletions, modifications, and substitutionsnot specifically described may be made without departing from the spiritand scope of the invention. Terminology used herein should not beconstrued as being “means-plus-function” language unless the term“means” is expressly used in association therewith.

REFERENCES

Each of the following is incorporated herein by reference, particularlyfor the teaching for which it was cited.

-   -   1. Y. Nanishi, Y. Saito, and T. Yamaguchi, Jpn. J. Appl. Phys.        42, 2549 (2003) and the references therein.    -   2. A. G. Bhuiyan, A. Hashimoto, and A. Yamamoto, J. Appl. Phys.        94, 2779 (2003).    -   3. N. Dietz, M. Alevli, V. Woods, M. Strassburg, H. Kang,        and I. T. Ferguson, Phys. Status Solidi B 242, 2985 (2005).    -   4. R. P. Bhatta, B. D. Thoms, A. Weerasekera, A. G. U.        Perera, M. Alevli, and N. Dietz, J. Vac. Sci. Technol. 25, 967        (2007).    -   5. Shou-Yi Kuo, Fang-I Lai, Wei-Chun Chen, Woei-Tyng Lin,        Chien-Nan Hsiao, Hsin-I Lin, and Han-Chang Pan, Diamond &        Related Materials 20, 1188 (2011).    -   6. M. A. Hafez and H. E. Elsayed-Ali, J. Vac. Sci. Technol. A        27, 696 (2009).    -   7. K. S. Boutros, F. G. McIntosh, J. C. Roberts, S. M.        Bedair, E. L. Piner, and N. A. El-Masry. Appl. Phys. Lett. 67,        1856 (1995).    -   8. C. Ozgit, I. Donmez, M. Alevli, and N. Biyikli, J. Vac. Sci.        Technol. A 30, 01A124 (2012).    -   9. N. H. Karam, T. Parodos, P. Colter, D. McNulty, W.        Rowland, J. Schetzina, N. El-Masry, and S. M. Bedair, Appl.        Phys. Lett. 67, 94 (1995).    -   10. K. Kim, N. Kwak, and S. Lee, Electron. Mater. Lett. 5, 83        (2009).    -   11. M. Alevli, C. Ozgit, I. Donmez, and N. Biyikli, Phys. Status        Solidi A 209, 266 (2012).    -   12. O. Ambacher, M. S. Brandt, R. Dimitrov, T. Metzger, M.        Stutzmann, R. A. Fischer, A. Miehr, A. Bergmaier, and G.        Dollinger, J. Vac. Sci. Technol. B 14, 3532 (1996). InN        dissociation temp 630    -   13. M. Y. Duan, L He, M. Xu, M. Y. Xu, Shuyan Xu, and K.        Ostrikov, Phys. Rev. B 81, 033102 (2010).    -   14. A. Yamamoto, T. Shin-ya, T. Sugiura, A. Hashimoto, J. Cryst.        Growth, 189/190, 461 (1998).    -   15. J. G. Lozano, F. M. Morales, R. Garcia, D. Gonzalez, V.        Lebedev, Ch. Y. Wang, V. Cimalla, and O Ambacher, Appl. Phys.        Lett. 90, 091901 (2007).    -   16. A. Janotti and C, G. Van de Walle, Appl. Phys. Lett. 92,        032104 (2008).    -   17. L. F. J. Piper, T. D. Veal, M. Walker, I. Mahboob, C. F.        McConville, H. Lu, and W. J. Schaff, J. Vac. Sci. Technol. A 23,        617 (2005)    -   18. C. G. Van de Walle, J. L. Lyons, and A. Janotti, Solidi A        207, 1024 (2010).    -   19. T. Matsuoka, H. Okamoto, M. Nakao, H. Harima, and E.        Kurimoto, Appl. Phys. Lett. 81, 1246 (2002).    -   20. M. C. Lee, H. C. Lin, Y. C. Pan, C. K. Shu, J. Ou, W. H.        Chen, and W. K. Chen, Appl. Phys. Lett. 73, 2606 (1998).    -   21. A. P. Lima, A. Tabata, J. R. Leite, S. Kaiser, D.        Schikora, B. Schottker, T. Frey, D. J. As, and K. Lischka, J.        Cryst. Growth, 201/202, 396 (1999).

What is claimed is:
 1. A method for growing crystalline, epitaxialindium nitride (InN) materials, the method comprising growing hexagonaland/or cubic InN using pulsed growth plasma-assisted atomic layerepitaxy at a temperature lower than 300° C. to obtain a material havingthe same crystal structure throughout.
 2. The method of claim 1, usingN₂ plasma as a nitrogen precursor.
 3. The method of claim 1, usingtrimethylindium as an indium precursor.
 4. The method of claim 1,wherein said hexagonal and/or cubic InN consists of a homogenous phaseof either hexagonal or cubic InN.
 5. The method of claim 1, wherein saidtemperature is intentionally varied during said growing in order tocontrol conductivity of said hexagonal and/or cubic InN.
 6. The methodof claim 1, further comprising in situ surface treatment with atomichydrogen, nitrogen, a mixture of hydrogen and nitrogen, and/or ammoniaplasma.
 7. The method of claim 1, further comprising variation of purgetime with the pumping speed, thereby controlling formation of carbonimpurities.
 8. The method of claim 1, wherein said temperature is lowerthan 200° C.
 9. The method of claim 8, using N₂ plasma as a nitrogenprecursor.
 10. The method of claim 8, wherein said hexagonal and/orcubic InN consists of a homogenous phase of either hexagonal or cubicInN.
 11. The method of claim 8, wherein said temperature isintentionally varied during said growing in order to controlconductivity of said hexagonal and/or cubic InN.
 12. The method of claim8, further comprising in situ surface treatment with atomic hydrogen,nitrogen, a mixture of hydrogen and nitrogen, and/or ammonia plasma. 13.The method of claim 8, further comprising variation of purge time withthe pumping speed, thereby controlling formation of carbon impurities.14. The method of claim 1, wherein said pulsed growth method comprisespulsed growth of an Al_(x)In_(1-x)N film at a temperature lower than300° C. by via alternate pulses of indium or aluminim precursor andnitrogen precursor.
 15. The method of claim 14, using N₂ plasma and/orammonia plasma as said nitrogen precursor.
 16. The method of claim 14,wherein said film has a homogenous phase.
 17. The method of claim 14,further comprising in situ surface treatment with atomic hydrogen,nitrogen, a mixture of hydrogen and nitrogen, and/or ammonia plasma. 18.The method of claim 14, further comprising variation of purge time withthe pumping speed, thereby controlling formation of carbon impurities.19. A material comprising InN in a face-centered cubic latticecrystalline structure having an NaCl type phase.
 20. The method of claim14, further comprising the use of a trimethylaluminum as an aluminumprecursor.